Method for producing a bio-based carpet material

ABSTRACT

The present invention includes a method for making a bio-based carpet material by providing tufts, a backing, a pre-coat, and a backing material wherein the pre-coat includes the reaction product of a pre-coat A-side having a pre-coat isocyanate and a pre-coat B-side and the backing material includes the reaction product of a backing material A-side having an isocyanate and a backing material B-side. The pre-coat B-side and the backing material B-side may include a polyol derived from petroleum; a vegetable oil, cross-linker, and a catalyst; or a transesterified polyol.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a divisional of U.S. patent application Ser. No.09/974,301, now issued as U.S. Pat. No. 6,962,636, entitled METHOD OFPRODUCING A BIO-BASED CARPET MATERIAL, by Thomas M. Kurth et al., filedon Oct. 10, 2001, the disclosure of which is hereby incorporated byreference in its entirety.

U.S. patent application Ser. No. 09/974,301, now issued as U.S. Pat. No.6,962,636, entitled METHOD OF PRODUCING A BIO-BASED CARPET MATERIAL, byThomas M. Kurth et al., filed on Oct. 10, 2001, is acontinuation-in-part of U.S. patent application Ser. No. 09/646,356,which has now issued as U.S. Pat. No. 6,465,569, entitled IMPROVEDCELLULAR PLASTIC MATERIAL, by Thomas M. Kurth, filed Sep. 14, 2000,which is the National Stage of International Application No.PCT/US99/21511, filed on Sep. 17, 1999, which is a continuation-in-partof U.S. patent application Ser. No. 09/154,340 filed on Sep. 17, 1998,which has now issued as U.S. Pat. No. 6,180,686, entitled IMPROVEDCELLULAR PLASTIC MATERIAL;

U.S. patent application Ser. No. 09/974,301, now issued as U.S. Pat. No.6,962,636, entitled METHOD OF PRODUCING A BIO-BASED CARPET MATERIAL, byThomas M. Kurth et al., filed on Oct. 10, 2001, is also acontinuation-in-part of U.S. patent application Ser. No. 09/944,212,entitled TRANSESTERIFIED POLYOL HAVING SELECTABLE AND INCREASEDFUNCTIONALITY AND URETHANE MATERIAL PRODUCTS FORMED USING THE POLYOL, byThomas M. Kurth et al., filed on Aug. 31, 2001, the disclosure of whichis hereby incorporated by reference in its entirety, which claimspriority to and the benefit of: (1) U.S. Provisional Patent ApplicationSer. No. 60/230,463, entitled TRANSESTERIFIED POLYOL HAVING SELECTABLEAND INCREASED FUNCTIONALITY AND URETHANE PRODUCTS FORMED USING THEPOLYOL, by Thomas M. Kurth et al., filed on Sep. 6, 2000, the disclosureof which is hereby incorporated by reference in its entirety; (2) U.S.Provisional Patent Application Ser. No. 60/239,161, entitledTRANSESTERIFIED POLYOL HAVING SELECTABLE AND INCREASED FUNCTIONALITY ANDURETHANE PRODUCTS FORMED USING THE POLYOL, by Thomas M. Kurth et al.,filed on Oct. 10, 2000, the disclosure of which is hereby incorporatedby reference in its entirety; and (3) U.S. Provisional PatentApplication Ser. No. 60/251,068, entitled TRANSESTERIFIED POLYOL HAVINGSELECTABLE AND INCREASED FUNCTIONALITY AND URETHANE PRODUCTS FORMEDUSING THE POLYOL, by Thomas M. Kurth et al., filed on Dec. 4, 2000, thedisclosure of which is hereby incorporated by reference in its entirety;

U.S. patent application Ser. No. 09/974,301, now issued as U.S. Pat. No.6,962,636, entitled METHOD OF PRODUCING A BIO-BASED CARPET MATERIAL, byThomas M. Kurth et al., filed on Oct. 10, 2001, also claims priority toand the benefit of 60/251,068, entitled TRANSESTERIFIED POLYOL HAVINGSELECTABLE AND INCREASED FUNCTIONALITY AND URETHANE PRODUCTS FORMEDUSING THE POLYOL, by Thomas M. Kurth et al., filed on Dec. 4, 2000; and

U.S. patent application Ser. No. 09/974,301, now issued as U.S. Pat. No.6,962,636, entitled METHOD OF PRODUCING A BIO-BASED CARPET MATERIAL, byThomas M. Kurth et al., filed on Oct. 10, 2001, also claims priority toand the benefit of 60/239,161, entitled TRANSESTERIFIED POLYOL HAVINGSELECTABLE AND INCREASED FUNCTIONALITY AND URETHANE PRODUCTS FORMEDUSING THE POLYOL, by Thomas M. Kurth et al., filed on Oct. 10, 2000.

BACKGROUND OF THE INVENTION

Because of their widely ranging mechanical properties and their abilityto be relatively easily machined and formed, plastic foams andelastomers have found wide use in a multitude of industrial and consumerapplications. In particular, urethane materials, such as foams andelastomers, have been found to be well suited for many applications.Automobiles, for instance, contain a number of components, such as cabininterior parts, that are comprised of urethane foams and elastomers.Urethane foams are also used as carpet backing. Such urethane foams aretypically categorized as flexible, semi-rigid, or rigid foams withflexible foams generally being softer, less dense, more pliable, andmore subject to structural rebound subsequent to loading than rigidfoams.

The production of urethane foams and elastomers are well known in theart. Urethanes are formed when isocyanate (NCO) groups react withhydroxyl (OH) groups. The most common method of urethane production isvia the reaction of a polyol and an isocyanate, which forms the backboneurethane group. A cross-linking agent and/or chain extender may also beadded. Depending on the desired qualities of the final urethane product,the precise formulation may be varied. Variables in the formulationinclude the type and amounts of each of the reactants and additives.

In the case of a urethane foam, a blowing agent is added to cause gas orvapor to be evolved during the reaction. The blowing agent is oneelement that assists in creating the size of the void cells in the finalfoam, and commonly is a solvent with a relatively low boiling point orwater. A low boiling solvent evaporates as heat is produced during theexothermic isocyanate/polyol reaction to form vapor bubbles. If water isused as a blowing agent, a reaction occurs between the water and theisocyanate group to form an amine and carbon dioxide (CO₂) gas in theform of bubbles. In either case, as the reaction proceeds and thematerial solidifies, the vapor or gas bubbles are locked into place toform void cells. Final urethane foam density and rigidity may becontrolled by varying the amount or type of blowing agent used.

A cross-linking agent is often used to promote chemical cross-linking toresult in a structured final urethane product. The particular type andamount of cross-linking agent used will determine final urethaneproperties such as elongation, tensile strength, tightness of cellstructure, tear resistance, and hardness. Generally, the degree ofcross-linking that occurs correlates to the flexibility of the finalfoam product. Relatively low molecular weight compounds with greaterthan single functionality are found to be useful as cross-linkingagents.

Catalysts may also be added to control reaction times and to effectfinal product qualities. The catalysts generally effect the speed of thereaction. In this respect, the catalyst interplays with the blowingagent to effect the final product density. Preferably, for foam urethaneproduction, the reaction should proceed at a rate such that maximum gasor vapor evolution coincides with the hardening of the reaction mass.The catalyst may also effect the timing or speed of curing so that aurethane foam may be produced in a matter of minutes instead of hours.

Polyols currently used in the production of urethanes are petrochemicalsbeing generally derived from propylene or ethylene oxides. Polyesterpolyols and polyether polyols are the most common polyols used inurethane production. For flexible foams, polyester or polyether polyolswith molecular weights greater than 2,500, are generally used. Forsemi-rigid foams, polyester or polyether polyols with molecular weightsof 2,000 to 6,000 are generally used, while for rigid foams, shorterchain polyols with molecular weights of 200 to 4,000 are generally used.There is a very wide variety of polyester and polyether polyolsavailable for use, with particular polyols being used to engineer andproduce a particular urethane elastomer or foam having desiredparticular final toughness, durability, density, flexibility,compression set ratios and modulus, and hardness qualities. Generally,higher molecular weight polyols and lower functionality polyols tend toproduce more flexible foams than do lower molecular weight polyols andhigher functionality polyols. In order to eliminate the need to produce,store, and use different polyols, it would be advantageous to have asingle, versatile, renewable component that was capable of being used tocreate final urethane foams of widely varying qualities.

Currently, one method employed to increase the reactivity of petroleumbased polyols includes propoxylation or ethoxylation. When propoxylationor ethoxylation is done on conventional petroleum based polyols, currentindustry practice is to employ about 70% propylene oxide by weight ofthe total weight of the polyol and propylene oxide is required tocomplete the reaction. Due to the large amount of alkyloxide typicallyused, the reaction if the alkyloxide and the petroleum based polyol isextremely exothermic and alkyloxides can be very expensive to use,especially in such high volumes. The exothermic nature of the reactionrequires numerous safety precautions be undertaken when the process isconducted on an industrial scale.

Use of petrochemicals such as, polyester or polyether polyols isdisadvantageous for a variety of reasons. As petrochemicals areultimately derived from petroleum, they are a non-renewable resource.The production of a polyol requires a great deal of energy, as oil mustbe drilled, extracted from the ground, transported to refineries,refined, and otherwise processed to yield the polyol. These requiredefforts add to the cost of polyols and to the disadvantageousenvironmental effects of its production. Also, the price of polyolstends to be somewhat unpredictable. Their price tends to fluctuate basedon the fluctuating price of petroleum.

Also, as the consuming public becomes more aware of environmentalissues, there are distinct marketing disadvantages to petrochemicalbased products. Consumer demand for “greener” products continues togrow. The term “bio-based” or “greener” polyols for the purpose of thisapplication is meant to be broadly interpreted to mean all polyols notderived exclusively from non-renewable resources. Petroleum andbio-based copolymers are also encompassed by the term “bio-based”. As aresult, it would be most advantageous to replace polyester or polyetherpolyols, as used in the production of urethane elastomers and foams,with more versatile, renewable, less costly, and more environmentallyfriendly components.

The difficulties in the past that occurred due to the use of vegetableoil as the polyols to produce a urethane product include the inabilityto regulate the functionality of the polyol resulting in variations inurethane product where the industry demands relatively strictspecifications be met and the fact that urethane products, in the past,outperformed vegetable oil based products in quality tests, such ascarpet backing pull tests.

An unresolved need therefore exists for an improved functionality,vegetable oil based polyol of increased and selectable functionality foruse in manufacturing urethane materials such as, elastomers and foams.Also needed is a method of producing such urethane materials, inparticular, carpet materials using the improved functionality, vegetableoil based polyol based on a reaction between isocyanates alone or as aprepolymer, in combination with the improved functionality polyol or ablend of the improved functionality polyol and other polyols includingpetrochemical based polyols. The products and methods of the presentinvention are particularly desirable because they relate to relativelyinexpensive, versatile, renewable, environmentally friendly materialssuch as, vegetable oil, blown soy oil, or transesterified vegetable oilthat forms a polyol of increased and selectable functionality that canbe a replacement for soy or petroleum based polyether or polyesterpolyols typically employed.

SUMMARY OF THE INVENTION

One aspect of the present invention includes a method of making a carpetmaterial providing tufts, a backing, a pre-coat, and a backing material.The pre-coat includes the reaction product of a pre-coat A-side having apre-coat isocyanate and a pre-coat B-side having a petroleum basedpolyol, a pre-coat cross-linking agent, and a pre-coat catalyst. Thebacking material includes the reaction product of a backing materialA-side having an isocyanate and a backing material B-side having avegetable oil, a cross-linking agent and a catalyst. The tufts areengaged with the primary backing thereby forming griege goods having atop and bottom surface. The pre-coat is applied onto the bottom surfaceof the griege goods and cured. The backing material is applied to thebottom surface of the griege goods.

Another aspect of the present invention includes the method of making acarpet material by providing tufts, a primary backing, a pre-coat and abacking material. The pre-coat includes the reaction product of apre-coat A-side having a pre-coat isocyanate and a pre-coat B-sidehaving a pre-coat petroleum based polyol. The backing material includesthe reaction product of a backing material A-side having a backingmaterial isocyanate and a backing material B-side having the reactionproduct of an esterified polyol and a backing material vegetable oilwhere the esterified polyol includes the reaction product of a firstmultifunctional compound and a second multifunctional compound. Thetufts are engaged with the primary backing thereby forming griege goodshaving a top surface and a bottom surface. The pre-coat is applied ontothe bottom surface of the griege goods and cured. The backing materialis applied to the bottom surface of the griege goods.

In yet another aspect of the present invention, a method of making acarpet material includes providing tufts, a primary backing material,and a pre-coat where the pre-coat material includes the reaction productof a pre-coat A-side having pre-coat isocyanate and a pre-coat B-sidehaving a pre-coat vegetable oil, a cross-linker, and a pre-coatcatalyst. The tufts are engaged with the primary backing thereby forminggriege goods having a top and bottom surface. The pre-coat is appliedonto the bottom surface of the griege goods and cured.

In still another embodiment of the present invention, the method ofmaking a carpet material includes providing tufts, a primary backingmaterial, and a pre-coat where the pre-coat includes the reactionproduct of a pre-coat A-side having a pre-coat isocyanate and a pre-coatB-side having the reaction product of a pre-coat esterified polyol and apre-coat vegetable oil. The pre-coat esterified polyol includes thereaction product of a first pre-coat multifunctional compound and asecond pre-coat multifunctional compound. The tufts are engaged with theprimary backing thereby forming griege goods having a top and bottomsurface. The pre-coat is applied onto the bottom surface of the griegegoods and cured.

These and other features, advantages and objects of the presentinvention will be further understood and appreciated by those skilled inthe art by reference to the following specification, claims, andappended drawings.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a simplified carpet processing line diagram of one embodimentof the present invention;

FIG. 2 is a simplified carpet processing line diagram of anotherembodiment of the present invention;

FIG. 3 is a simplified carpet processing line diagram of anotherembodiment of the present invention;

FIG. 4 is a simplified carpet processing line diagram of anotherembodiment of the present invention; and

FIG. 5 is a flowchart of the general carpet processing steps.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

A new vegetable oil based polyol having increased and selectablefunctionality has been developed. A two-stage transesterificationprocess produces the new vegetable oil based polyol as the reactionproduct of a multifunctional alcohol and a multifunctional component,subsequently reacted with a vegetable oil. In the first step in thetwo-stage transesterification process, glycerin, a suitablemultifunctional alcohol, or other suitable multifunctional alcohol isheated to about 230° F., and advantageously also stirred; however, acatalyst may be used instead of or in addition to heat. Next, amultifunctional component having at least two hydroxyl groups preferablyincludes a saccharide compound, typically a monosaccharide,disaccharide, a polysaccharide, sugar alcohol, cane sugar, honey, ormixture thereof is slowly introduced into the glycerin until saturated.Currently, the preferred saccharide components are fructose and canesugar. Cane sugar provides greater tensile strength and fructoseprovides greater elongation of the carbon chain of the polyol.Preferably, 2 parts of the saccharide compound is added to 1 part of themultifunctional alcohol, by weight. Glycerin is a carrier for thesaccharide compound component, although it does add some functionalhydroxyl groups. The saccharide component is slowly added until noadditional saccharide component can be added to the glycerin solution.

It is believed that the multifunctional alcohol and the saccharidecomponent undergo an initial transesterification to form new esterproducts (precursors). As such, the functionality of the new polyol isselectable. The greater the functionality of the alcohol, the greaterthe functionality of the final new polyol.

Next, from about 200 to 300 grams (experimental amount) of vegetableoil, preferably soy oil, and most preferably blown soy oil, is heated toat least about 180° F. However, the temperature may be any temperaturefrom about 180° F. until the oil is damaged. Blown soy oil providessuperior results to regular vegetable oil; however, any vegetable oil orblown vegetable oil will work. Other vegetable oils that may be utilizedin the present invention include, but should not be limited to, palmoil, safflower oil, sunflower oil, canola oil, rapeseed oil, cottonseedoil, linseed, and coconut oil. When these vegetable oils are used, theytoo are preferably blown. However, the vegetable oils may be crudevegetable oils or crude vegetable oils that have had the soap stock andwax compound in the crude oil removed.

Once the blown soy oil has been heated, it is slowly reacted with theheated glycerin/saccharide ester, the first transesterification reactionproduct. The vegetable oil and the first transesterification productundergo a second transesterification reaction that increases thefunctionality of the resulting polyol. Lowering the amount of thesaccharide component added to the vegetable oil lowers the number offunctional groups available to be cross-linked with an isocyanate groupwhen the polyol produced using the two-stage transesterification processoutlined above is used to create a urethane product. In this manner,functionality of the final polyol produced by the transesterificationprocess of the present invention may be regulated and engineered.Therefore, more rigid urethane products are formed using a polyolproduced by the present invention by using increased amounts of asaccharide component. In addition, as discussed above, the higherfunctionality of the multifunctional alcohol may also increase thefunctionality of the urethane products formed using the new polyol.

Also, polyols having increased functionality can not only be made by thetransesterification process discussed above alone, but a furtherincrease in functionality of the vegetable oil based polyol may also beachieved by propoxylation, butyoxylation, or ethoxylation. Applicantsbelieve that the addition of propylene oxide (propoxylation), ethyleneoxide (ethoxylation), butylene oxide, (butyloxylation), or any otherknown alkene oxides to a vegetable oil, a crude vegetable oil, a blownvegetable oil, the reaction product of the saccharide (multifunctionalcompound) and the multifunctional alcohol, or the final vegetable oilbased, transesterified polyol produced according to thetransesterification process discussed above will further increase thefunctionality of the polyol thereby formed.

Also, polyols having increased functionality can not only be made by thetransesterification process discussed above alone, but a furtherincrease in functionality of a vegetable oil based polyol may also beachieved by oxylation (propoxylation, butyoxylation, or ethoxylation).The addition of propylene oxide (propoxylation), ethylene oxide(ethoxylation), butylene oxide, (butyloxylation), or any other knownalkene oxides to a vegetable oil, a crude vegetable oil, a blownvegetable oil, the reaction product of the saccharide (multifunctionalcompound) and the multifunctional alcohol, or the final vegetable oilbased, transesterified polyol produced according to thetransesterification process discussed above will further increase thefunctionality of the polyol thereby formed.

Applicants currently believe that bio-based oxylation substances, suchas, tetrahydrofuran (TMF), tetrahydrofurfuryl, tetrahydrofurfural, andfurfural derivatives as well as tetrahydrofurfuryl alcohol may be usedinstead of or in addition to alkyloxides in the present invention.

Moreover, Applicants believe that any substance containing an activehydrogen may be oxylated to any desired degree and subsequentlytransesterified. Once transesterified with the vegetable oil, a compoundwhose active hydrogens were not fully oxylated may be further oxylated.Some active hydrogens include OH, SH, NH, chorohydrin, or any acidgroup. Compounds containing these active hydrogens, such as ethylenediamine, may be partially (because it contains more than one activehydrogen) or fully oxylated and then transesterified with themultifunctional alcohol, a crude vegetable oil, a blown vegetable oil,the reaction product of the saccharide (multifunctional compound) andthe multifunctional alcohol, or the final vegetable oil based,transesterified polyol produced according to the transesterificationprocess discussed above will further increase the functionality of thepolyol thereby formed.

When propoxylation or like reactions are done to the vegetable oil orthe transesterified polyol, an initiator/catalyst is typically employedto start and, throughout the reaction, to maintain the reaction of thepropylene oxide and the vegetable oil to the transesterified polyol. Theresulting reaction is an exothermic reaction. Initiators/catalysts thatmay be employed in the propoxylation, ethyloxylation, or butyloxylationreaction include triethylamine, trimethylamine, or other suitable aminesas well as potassium hydroxide or other suitable metal catalyst.

Significantly, while about 70% by weight of alkyloxides is typicallyused to fully oxylate a petroleum based polyol, when oxylation of crude,blown, or transesterified vegetable based polyols is conducted, onlyabout 5% to about 10% of the oxylation compound is necessary. As aresult, Applicants have found that, in experimental amounts, thereaction is not nearly as exothermic as a “typical” oxylation reactionusing a petroleum based product. As a result, Applicants believe thiswill be a significant safety benefit when done at production scale.Applicants have surprisingly found that adding heat to the oxylationreaction employing a vegetable based polyol is preferred. On anindustrial scale, this may provide the additional benefit of regulatingreaction time. Obviously, since significantly less oxylation rawmaterial is used when oxylation is done to the vegetable based polyol ofthe present invention, significant cost savings result as well.Additionally and probably most significantly, oxylation of the vegetablebased polyols of the present invention, either blown or transesterified,results in a vegetable oil based polyol with improved reactive andchemical properties.

In practice, the alkyloxide or bio-based oxylation compound and asuitable catalyst/initiator are added to a vegetable oil, preferably ablown or transesterified vegetable oil and mixed. The resultant mixtureis then heated until the temperature reaches about 100° C. Thetemperature is held at about 100° C. for about one to about two hours.The mixture is then cooled to ambient temperature while pulling a vacuumto remove any excess alkyloxide or bio-based oxylation compound.

Moreover, it has been contemplated that the above describedtransesterification process may be performed on crude or non-blownvegetable (soy) oil prior to blowing the vegetable (soy) oil to form apre-transesterified vegetable (soy) oil. The pre-transesterifiedvegetable (soy) oil may then be blown, as known, to increase itsfunctionality. Thereafter, the transesterification process discussedabove may optionally be carried out again on the blownpre-transesterified vegetable (soy) oil.

A transesterification catalyst such as tetra-2-ethylhexyl titonate,which is marketed by DUPONT® as TYZOR® TOT, may be used, instead of orin addition to heat. Also, known acids and other transesterificationcatalysts known to those of ordinary skill may also be used.

The preparation of urethanes is well known in the art. They aregenerally produced by the reaction of petrochemical polyols, eitherpolyester or polyether, with isocyanates. The flexibility or rigidity ofthe foam is dependent on the molecular weight and functionality of thepolyol and isocyanate used.

Petrochemical polyol based polyurethanes can be prepared when what isknown in the art as an A-side reactant is combined with what is known inthe art as a B-side reactant. The A-side reactant of the urethane of theinvention comprises an isocyanate, typically a diisocyanate such as:4,4′ diphenylmethane diisocyanate; 2,4 diphenylmethane diisocyanate; andmodified diphenylmethane diisocyanate. Typically, a modifieddiphenylmethane diisocyanate is used. MONDUR MR LIGHT®, an aromaticpolymeric isocyanate based on diphenylmethane-diisocyanate, and MONDUR®MA-2903, a new generation MDI prepolymer, manufactured by BAYER®Corporation, are two specific examples of possible isocyanates that canbe used. It should be understood that mixtures of different isocyanatesmay also be used. The particular isocyanate or isocyanate mixture usedis not essential and can be selected for any given purpose or for anyreason as desired by one of ordinary skill in the art.

The A-side of the reaction may also be a prepolymer isocyanate. Theprepolymer isocyanate is the reaction product of an isocyanate,preferably a diisocyanate, and most preferably some form ofdiphenylmethane diisocyanate (MDI) and a vegetable oil. The vegetableoil can be any of the vegetables discussed previously or any other oilhaving a suitable number of reactive hydroxyl (OH) groups. Soy oil isparticularly advantageous to use. To create the prepolymer diisocyanate,the vegetable oil, the transesterified vegetable oil or a mixture ofvegetable oils and transesterified vegetable oils are mixed and allowedto react until the reaction has ended. There may be some unreactedisocyanate (NCO) groups in the prepolymer. However, the total amount ofactive A-side material has increased through this process. Theprepolymer reaction reduces the cost of the A-side component bydecreasing the amount of isocyanate required and utilizes a greateramount of inexpensive, environmentally friendly vegetable (soy) oil.Alternatively, after the A-side prepolymer is formed, additionalisocyanates may be added.

The B-side material is generally a solution of a petroleum basedpolyester or polyether polyol, cross-linking agent, and blowing agent. Acatalyst is also generally added to the B-side to control reaction speedand effect final product qualities. As discussed infra, the use of apetrochemical such as, a polyester or polyether polyol is undesirablefor a number of reasons.

It has been discovered that urethane materials of high quality can beprepared by substituting the petroleum based polyol in the B-sidepreparation with the increased and selectable functionality polyolproduced by the transesterification process outlined above. UsingApplicants' method permits substantial regulation of the functionalityof the resulting polyol thereby making the polyols produced byApplicants' new process more desirable to the industry. Previously, thefunctionality of vegetable oil based polyols varied dramatically due to,for example, genetic or environmental reasons.

In addition to the increased and selectable functionality polyolproduced by the transesterification process outlined above, the B-sideof the urethane reaction may include a cross-linking agent.Surprisingly, a cross-linking agent is not required when using the newtransesterified polyol to form a urethane product. Typically, a blowingagent and a catalyst are also used in the B-side of the reaction. Thesecomponents are also optional, but are typically used to form urethaneproduct, especially foams.

A currently preferred blown soy oil typically has the followingcomposition; however, the amounts of each component vary over a widerange. These values are not all inclusive. Amounts of each components ofthe oil vary due to weather conditions, type of seed, soil quality andvarious other environmental conditions:

100% Pure Soybean Oil Air Oxidized Moisture 1.15% Free Fatty Acid 1-6%,typically ≈ 3% Phosphorous 50-200 ppm Peroxide Value 50-290 Meq/Kg Iron≈6.5 ppm (naturally occurring amount) Hydroxyl Number 42-220 mg KOH/gAcid Value 5-13 mg KOH/g Sulfur ≈200 ppm Tin <.5 ppm

Blown soy oil typically contains a hydroxyl value of about 100-180 andmore typically about 160, while unblown soy oil typically has a hydroxylvalue of about 30-40. The infrared spectrum scans of two samples of thetype of blown soy oil used in the present invention are shown in FIGS. 1and 2. Blown soy oil and transesterified soy oil produced according tothe present invention have been found to have a glass transition atabout −137° C. to about −120° C. depending on the saccharide componentused and whether one is used at all. The glass transition measures thefirst signs of molecular movement in the polymer at certaintemperatures. The glass transition can be measured using a DynamicMechanical Thermal (DMT) analysis machine. Rheometric Scientific is onemanufacturer of DMT machines useful with the present invention.Applicants specifically utilize a DMTA5 machine from RheometricScientific.

Applicants have also found that soybean oil and most other vegetableoils have C₃ and C₄ acid groups, which cause bitter smells when thevegetable polyols are reacted with isocyanates. In order to remove theseacid groups and the resultant odor from the end use product, Applicantshave also developed a way to effectively neutralize these lowering acidswith the functionality of the polyol.

Applicants blow nitrogen (N₂) through a solution of about 10% ammoniumhydroxide. Nitrogen gas was selected because it does not react with theammonium hydroxide. Any gas that does not react with the ammoniumhydroxide while still mixing the ammonium hydroxide through thevegetable oil would be acceptable. The ammonium hydroxide neutralizesacid groups that naturally occur in the vegetable oil. The pH oftransesterified, blown, and crude vegetable oil typically falls withinthe range of from about 5.9-6.2. Vegetable oil neutralized by theabove-identified process has a typical pH range of from about 6.5 toabout 7.2, but more typically from about 6.7 to 6.9. The removal ofthese C₃ and C₄ acid groups results in a substantial reduction in odorwhen the neutralized polyols are used to form isocyanates.

Except for the use of the transesterified polyol replacing the petroleumbased polyol, the preferred B-side reactant used to produce urethanefoam is generally known in the art. Accordingly, preferred blowingagents, which may be used for the invention, are those that are likewiseknown in the art and may be chosen from the group comprising 134A HCFC,a hydrochloroflurocarbon refrigerant available from Dow Chemical Co. ofMidland, Mich.; methyl isobutyl ketone (MIBK); acetone; ahydroflurocarbon; cyclopentane; methylene chloride; any hydrocarbon; andwater or mixtures thereof. Presently, a mixture of cyclopentane andwater is preferred. Another possible blowing agent is ethyl lactate,which is derived from soybeans and is bio-based. At present, water isthe preferred blowing agent when a blowing agent is used. The blowingagents, such as water, react with the isocyanate (NCO) groups, toproduce a gaseous product. The concentrations of other reactants may beadjusted to accommodate the specific blowing agent used in the reaction.

As discussed above, when blown soy oil is used to prepare thetransesterified polyol of the B-side, the chain extender (cross-linkingagent) may be removed from the B-side of the urethane reactions andsimilar properties to urethane products produced using soy oil accordingto the teachings of WO 00/15684 and U.S. Pat. No. 6,180,686, thedisclosures of which are hereby incorporated by reference, are achieved.

If cross-linking agents are used in the urethane products of the presentinvention, they are also those that are well known in the art. They mustbe at least di-functional (a diol). The preferred cross-linking agentsfor the foam of the invention are ethylene glycol; 1,4 butanediol;diethanol amines; ethanol amines; tripropylene glycol, however, otherdiols and triols or greater functional alcohols may be used. It has beenfound that a mixture of tripropylene glycol; 1,4 butanediol; anddiethanol amines are particularly advantageous in the practice of thepresent invention. Dipropylene glycol may also be used as across-linking agent. Proper mixture of the cross-linking agents cancreate engineered urethane products of almost any desired structuralcharacteristics.

In addition to the B-side's vegetable oil, the optional blowingagent(s), and optional cross-linking agents, one or more catalysts maybe present. The preferred catalysts for the urethanes of the presentinvention are those that are generally known in the art and are mostpreferably tertiary amines chosen from the group comprising DABCO 33-LV®comprised of 33% 1,4 diaza-bicyclco-octane (triethylenediamine) and 67%dipropylene glycol, a gel catalyst available from the Air ProductsCorporation; DABCO® BL-22 blowing catalyst available from the AirProducts Corporation; POLYCAT® 41 trimerization catalyst available fromthe Air Products Corporation; Dibutyltin dilaurate; Dibutyltindiacetate; stannous octane; Air Products' DBU® (1,8 Diazabicyclo [5.4.0]dibutyltin dilaurate); and Air Products' DBU® (1,8 Diazabicyclo [5.4.0]dibutyltin diacetate). Other amine catalysts, including any metalcatalysts, may also be used and are known by those of ordinary skill inthe art.

Also as known in the art, when forming foam urethane products, theB-side reactant may further comprise a silicone surfactant whichfunctions to influence liquid surface tension and thereby influence thesize of the bubbles formed and ultimately the size of the hardened voidcells in a final urethane foam product. This can effect foam density andfoam rebound (index of elasticity of foam). Also, the surfactant mayfunction as a cell-opening agent to cause larger cells to be formed inthe foam. This results in uniform foam density, increased rebound, and asofter foam.

A molecular sieve may further be present to absorb excess water from thereaction mixture. The preferred molecular sieve of the present inventionis available under the trade name L-PASTE™.

The urethane materials (products) of the present invention are producedby combining the A-side reactant with the B-side reactant in the samemanner as is generally known in the art. Advantageously, use of thetransesterified polyol to replace the petroleum based polyol does notrequire significant changes in the method of performing the reactionprocedure. Upon combination of the A and B side reactants, an exothermicreaction ensues that may reach completion in anywhere from a few seconds(approximately 2-4) to several hours or days depending on the particularreactants and concentrations used. Typically, the reaction is carriedout in a mold or allowed to free rise. The components may be combined indiffering amounts to yield differing results, as will be shown in theExamples presented below.

A petroleum based polyol such as polyether polyol (i.e., Bayercorporation's MULTRANOL® 3901 polyether polyol and MULTRANOL® 9151polyether polyol), polyester polyol, or polyurea polyol may besubstituted for some of the transesterified polyol in the B-side of thereaction, however, this is not necessary. This preferred B-sideformulation is then combined with the A-side to produce a urethanematerial. The preferred A-side, as discussed previously, is comprised ofmethylenebisdiphenyl diisocyanate (MDI) or a prepolymer comprised of MDIand a vegetable oil, preferably soy oil or a prepolymer of MDI and thetransesterified polyol.

Flexible urethane foams may be produced with differing final qualitiesby not only regulating the properties of the transesterified polyol, butby using the same transesterified polyol and varying the particularother reactants chosen. For instance, it is expected that the use ofrelatively high molecular weight and high functionality isocyanates willresult in a less flexible foam than will use of a lower molecular weightand lower functionality isocyanate when used with the sametransesterified polyol. Likewise, as discussed earlier, the higher thefunctionality of the polyol produced by the transesterification process,the more rigid the foam produced using it will be. Moreover, it has beencontemplated that chain extenders may also be employed in the presentinvention. For example, butanediol, in addition to acting as across-linker, may act as a chain extender.

Urethane elastomers can be produced in much the same manner as urethanefoams. It has been discovered that useful urethane elastomers may beprepared using the transesterified polyol to replace some of or all ofthe petroleum based polyester or the polyether polyol. The preferredelastomer of the invention is produced using diphenylmethanediisocyanate (MDI) and the transesterified polyol. A catalyst may beadded to the reaction composition. The resulting elastomer has anapproximate density of about 52 lb. to about 75 lb. per cubic foot.

The following examples are the preparation of transesterified polyol ofthe present invention, as well as foams and elastomers of the inventionformed using the transesterified polyol. The examples will illustratevarious embodiments of the invention. The A-side material in thefollowing examples is comprised of modified diphenylmethane diisocyanate(MDI), unless otherwise indicated; however, any isocyanate compoundcould be used.

Also, “cure,” if used in the following examples, refers to the final,cured urethane product taken from the mold. The soy oil used in thefollowing examples is blown soy oil. Catalysts used include “DABCO33-LV®,” comprised of 33% 1,4-diaza-bicyclo-octane and 67% dipropyleneglycol available from the Air Products Urethanes Division; “DABCO®BL-22,” a tertiary amine blowing catalyst also available from the AirProducts Urethanes Division; “POLYCAT® 41” (n, n′, n″,dimethylamino-propyl-hexahydrotriazine tertiary amine) also availablefrom the Air Products Urethanes Division; dibutyltin dilaurate (T-12);dibutyltin diacetate (T-1); and Air Products DBU® (1,8 Diazabicyclo[5.4.0]). The structures of the Air Products DBU®'s (1,8 Diazabicyclo[5.4.0]) used in the present invention are shown in FIG. 4.

A blowing catalyst in the following examples effects the timing of theactivation of the blowing agent. Some of the examples may include“L-PASTE™,” which is a trade name for a molecular sieve for absorbingwater. Some may also contain “DABCO® DC-5160” or “Air Products DC193®”,both are silicone surfactants available from Air Products UrethaneDivision.

EXAMPLES

All percentages referred to in the following examples refer to weightpercent, unless otherwise noted.

Example 1

Transesterification 2.5% Glycerin 5.0% Sorbitol 92.5% Polyurea polyoland Blown soy oil mixture

Elastomer Formation B-side: 97 g Transesterified polyol formed above AirProducts DBU ® = urethane catalyst (1,8 Diazabicyclo[5.4.0]) 3%Butanediol (cross-linker) A-side: Modified monomeric MDI (MONDUR ®MA-2903)

The B-side was combined with the A-side in a ratio of 55 parts A-side to100 parts B-side.

Example 2

Transesterification 2.5% Glycerin 5.0% Sorbitol 92.5% Polyurea polyoland Blown soy oil

Elastomer Formation B-side: 97% Transesterified polyol formed above AirProducts DBU ® = urethane catalyst (1,8 Diazabicyclo[5.4.0])  3%Dipropylene glycol (chain extender) A-side: Modified monomeric MDI(MONDUR ® MA-2903)

The B-side was combined with the A-side in a ratio of 46 parts A-side to100 parts B-side.

Example 3

Transesterification 2.5% Glycerin 5.0% Sorbitol 92.5% Blown soy oil

Elastomer Formation B-side: 97% Transesterified polyol formed above AirProducts DBU ® = urethane catalyst (1,8 Diazabicyclo[5.4.0])  3%Dipropylene glycol A-side: Modified monomeric MDI (MONDUR ® MA-2903)

The B-side was combined with the A-side in a ratio of 61 parts A-side to100 parts B-side.

Example 4

Transesterification 5.0% Glycerin 10.0% Sorbitol 85.0% Blown soy oil

Elastomer Formation B-side: 97% Transesterified polyol formed above AirProducts DBU ® = urethane catalyst (1,8 Diazabicyclo[5.4.0])  3%Dipropylene glycol A-side: Modified monomeric MDI (MONDUR ® MA-2903)

The B-side was combined with the A-side in a ratio of 61 parts A-side to100 parts B-side.

Example 5

Transesterification 10.0% Glycerin 20.0% Sorbitol 70.0% Blown soy oil

Elastomer Formation B-side: Transesterified polyol formed above AirProducts DBU ® = urethane catalyst (1,8 Diazabicyclo[5.4.0]) 3.0 gDipropylene glycol A-side: Modified monomeric MDI (MONDUR ® MA-2903)

The B-side was combined with the A-side in a ratio of 61 parts A-side to100 parts B-side.

Example 6

Transesterification 12.0% Glycerin 24.0% Sorbitol 12.0% Polyurea polyol52.0% Blown soy oil

Elastomer Formation B-side: Transesterified polyol formed above Heat(190° F.) was used to catalyze the reaction Butanediol (cross-linker)A-side: Modified monomeric MDI (MONDUR ® MA-2903)

Example 7

Transesterification 5.0% Glycerin 10.0%  Sorbitol  85% Polyurea polyoland Blown soy oil mixture

Elastomer Formation B-side: 40.0 g Transesterified polyol formed above 0.3 g Air Products DBU ® = urethane catalyst (1,8 Diazabicyclo [5.4.0])10.0 g Polyether polyol (Bayer MULTRANOL ® 9151)  3.0 g Dipropyleneglycol A-side: Modified monomeric MDI (MONDUR ® MA-2903)

The B-side was combined with the A-side in a ratio of 38 parts A-side to100 parts B-side.

Example 8

Transesterification 5.0% Glycerin 10.0%  Sorbitol  85% Polyurea polyoland Blown soy oil mixture

Elastomer Formation B-side: 30.0 g Transesterified polyol formed above20.0 g Polyether polyol (Bayer MULTRANOL ® 9151)  3.0 g Air ProductsDBU ® = urethane catalyst (1,8 Diazabicyclo[5.4.0])  3.0 g Dipropyleneglycol A-side: Modified monomeric MDI (MONDUR ® MA-2903)

The B-side was combined with the A-side in a ratio of 31 parts A-side to100 parts B-side.

Example 9

Transesterification 5.0% Glycerin 10.0% Sorbitol 85.0% Blown soy oil

Elastomer Formation B-side: 50.0 g  Transesterified polyol formed above0.4 g Air Products DBU ® = urethane catalyst (1,8 Diazabicyclo[5.4.0])3.0 g Dipropylene glycol A-side: Modified monomeric MDI (MONDUR ®MA-2903)

The B-side was combined with the A-side in a ratio of 60 parts A-side to100 parts B-side.

Example 10

Transesterification 5.0% Glycerin 10.0% Sorbitol 5.0% Polyurea polyol80.0% Blown soy oil

Elastomer Formation B-side: 40.0 g  Transesterified polyol formed above0.4 g Air Products DBU ® = urethane catalyst (1,8 Diazabicyclo[5.4.0])2.4 g Dipropylene glycol A-side: Modified monomeric MDI (MONDUR ®MA-2903)

The B-side was combined with the A-side in a ratio of 40 parts A-side to100 parts B-side.

Example 11

Transesterification 5.0% Glycerin 10.0% Sorbitol 5.0% Polyurea polyol80.0% Blown soy oil

Elastomer Formation B-side: 40.0 g  Transesterified polyol formed above0.4 g Air Products DBU ® = urethane catalyst (1,8 Diazabicyclo[5.4.0])2.4 g Dipropylene glycol A-side: Modified monomeric MDI (MONDUR ®MA-2903)

The B-side was combined with the A-side in a ratio of 100 parts A-sideto 100 parts B-side.

Example 12

Transesterification 5.0% Glycerin 10.0% Sorbitol 12.0% Polyurea polyol73.0% Blown soy oil

Elastomer Formation B-side: 50.0 g  Transesterified polyol formed above0.4 g Air Products DBU ® = urethane catalyst (1,8 Diazabicyclo[5.4.0])3.0 g Dipropylene glycol A-side: Modified monomeric MDI (MONDUR ®MA-2903)

The B-side was combined with the A-side in a ratio of 61 parts A-side to100 parts B-side and cured at a temperature of 162° F.

Example 13

Transesterification 5.0% Glycerin 10.0% Sorbitol 85.0% Blown soy oil

Elastomer Formation B-side: 50.0 g  Transesterified polyol formed above0.4 g Air Products DBU ® = urethane catalyst (1,8 Diazabicyclo[5.4.0])3.0 g Dipropylene glycol A-side: Modified monomeric MDI (MONDUR ®MA-2903)

The B-side was combined with the A-side in a ratio of 80 parts A-side to100 parts B-side and cured at a temperature of 166° F.

Example 14

Transesterification 5.0% Glycerin 10.0% Sorbitol 85.0% Blown soy oil

Elastomer Formation B-side: 50.0 g  Transesterified polyol formed above0.4 g Dibutyltin diacetate (T-1) - catalyst 3.0 g Dipropylene glycolA-side: Modified monomeric MDI (MONDUR ® MA-2903)

The B-side was combined with the A-side in a ratio of 61 parts A-side to100 parts B-side and cured at a temperature of 153° F.

Example 15

Transesterification 1.0% (6.66 g) Glycerin 3.0% (13.4 g) Sorbitol 400.0g  Blown soy oil

This mixture was heated at 196° F. for 1.5 hours.

Example 16

20.0 g of Glycerin heated and stirred at 178° F.

Introduced 40.0 g sorbitol slowly for about 4 minutes

Stayed milky until about 15 minute mark

At temperatures above 120° F., the solution was very fluid and clear. Attemperatures under 120° F., the solution was clear; however, it was veryviscous.

Added this mixture to 200.0 g of blown soy oil

200.0 g of blown soy oil heated to 178° F.

Introduced sorbitol, glycerin mixture as follows:

Added 10.0 g turned very cloudy within 30 seconds. Could not see thebottom of the beaker

-   -   Still very cloudy after 5 minutes and added 10.0 g    -   Viscosity increased and had to reduce paddle speed after 10        minutes    -   Viscosity reduced somewhat after about 18 minutes        -   A further reduction in viscosity after about 21 minutes

This was mixed in a 500 ML beaker with a magnetic paddle. The scientistswere not able to see through the beaker. After about 21 minutes, avortex appended in the surface indicating a further reduction inviscosity. At this time, the mixture lightened by a visible amount.Maintained heat and removed.

Reacted the new polyol with Modified Monomeric MDI, NCO-19.

New Polyol 100% DBU 0.03% MDI 50 p to 100 p of about Polyol

Reaction:

-   -   Cream time about 30 seconds    -   Tack free in about 45 seconds    -   Good physical properties after about 2 minutes

The reaction looked good; the material showed no signs of blow andseemed to be a good elastomer. It does however exhibit some signs of toomuch crosslinking and did not have the amount of elongation that wouldbe optimal.

A comparative reaction run along side with the unmodified blown soy oilwas not tack free at 24 hours.

Example 17

Transesterification 1.0% Glycerin 3.0% Sorbitol 96.0% Blown soy oil

Elastomer Formation B-side: 50.0 g  Transesterified polyol formed as inExample 15 0.5 g Dibutyltin diacetate (T1) - catalyst 3.0 g Dipropyleneglycol A-side: Modified monomeric MDI (MONDUR ® MA-2903)

The B-side was combined with the A-side in a ratio of 61 parts A-side to100 parts B-side and cured at a temperature of 154° F. for 4 minutes.

Example 18

B-side: 50.0 g Transesterified polyol formed from 20 g DipropyleneGlycol, 5 g Glycerin, and 20 g sorbitol blended with 200 g blown soy oil 0.3 g Air Products DBU ® = urethane catalyst (1,8 Diazabicyclo[5.4.0])A-side: Modified monomeric MDI (MONDUR ® MA-2903)

The B-side was combined with the A-side in a ratio of 61 parts A-side to100 parts B-side.

Example 19

Transesterification 750 g Blown soy oil 150 g Glycerin  75 g Cane sugar

Example 20

B-side: 40.0 g  Transesterified polyol formed as in Example 19 10.0 g Polyether polyol (Bayer MULTRANOL ® 9151) 1.5 g Dipropylene Glycol 1.5 gButanediol 0.6 g Dibutyltin diacetate A-side: Modified monomeric MDI(MONDUR ® MA-2903)

The B-side was combined with the A-side in a ratio of 57 parts A-side to100 parts B-side and was set up on 20 seconds.

Example 21

B-side: 50.0 g  Transesterified polyol formed as in Example 19 10.0 g Polyether polyol (Bayer MULTRANOL ® 9151) 1.5 g Dipropylene Glycol 1.5 gButanediol 0.6 g Dibutyltin diacetate (T1) A-side: Modified monomericMDI (MONDUR ® MA-2903)

The B-side was combined with the A-side in a ratio of 71 parts A-side to100 parts B-side.

Example 22

B-side: 40.0 g  Transesterified polyol formed as in Example 19 10.0 g Polyether polyol (Bayer MULTRANOL ® 9151) 1.5 g Dipropylene Glycol 1.5 gButanediol 0.6 g Dibutyltin diacetate (T1) A-side: Modified monomericMDI (MONDUR ® MA-2903)

The B-side was combined with the A-side in a ratio of 45 parts A-side to100 parts B-side.

Example 23

B-side: 100.0 g Transesterified polyol formed as in Example 19 20.0 gPolyether polyol (Bayer MULTRANOL ® 9151) 3.0 g Dipropylene Glycol 3.0 gButanediol 0.7 g Dibutyltin diacetate (T1) 228.6 calcium carbonatefiller A-side: Modified monomeric MDI (MONDUR ® MA-2903)

The B-side was combined with the A-side in a ratio of 25 parts A-side to100 parts B-side.

Example 24

B-side: 20.0 g  Transesterified polyol formed as in Example 19 5.0 gTransesterification from Example 25 0.6 g Dipropylene Glycol 0.7 g AirProducts DBU ® = urethane catalyst (1,8 Diazabicyclo[5.4.0]) A-side:Modified monomeric MDI (MONDUR ® MA-2903).

The B-side was combined with the A-side in a ratio of 57 parts A-side to100 parts B-side and was set up on 20 seconds.

Example 25

Transesterification 100 g Blown soy oil  27 g 63% glycerin and 37% canesugar reaction product mixture

The above was heated at a temperature of 230° F. and mixed for 15minutes.

Example 26

Transesterification 100.0 g Blown soy oil  13.5 g 63% glycerin and 37%cane sugar reaction product mixture

The above was heated at a temperature of 220° F.

Example 27

Transesterification 400 g Blown soy oil  12 g 33% Glycerin and 66%Sorbitol

The glycerin and sorbitol product was preheated to 195° F. The totalmixture was heated for 15 minutes at 202° F.

Example 28

B-side: 50.0 g  Transesterified polyol formed as in Example 27 3.0 gDipropylene glycol 0.5 g Dibutyltin diacetate (T1) - catalyst A-side:Modified monomeric MDI (MONDUR ® MA-2903)

The B-side was combined with the A-side in a ratio of 61 parts A-side to100 parts B-side at a temperature of 134° F. for 4 minutes.

Example 29

B-side: 50.0 g  Transesterified polyol formed as in Example 27 3.0 gDipropylene glycol 0.8 g Dibutyltin diacetate (T1) - catalyst A-side:Modified monomeric MDI (MONDUR ® MA-2903)

The B-side was combined with the A-side in a ratio of 67 parts A-side to100 parts B-side.

Example 30

B-side: 50.0 g  Transesterified polyol formed as in Example 27 3.0 gDipropylene glycol 1.5 g Water 0.8 g Dibutyltin diacetate (T1) -catalyst A-side: Modified monomeric MDI (MONDUR ® MA-2903)

The B-side was combined with the A-side in a ratio of 90 parts A-side to100 parts B-side.

Example 31

B-side: 50.0 g  Transesterified polyol formed as in Example 27 3.0 gDipropylene glycol 1.5 g Water 0.8 g Dibutyltin diacetate (T1) -catalyst 0.2 g Silicon surfactant (AIR PRODUCTS ® DC193) A-side:Modified monomeric MDI (MONDUR ® MA-2903)

The B-side was combined with the A-side in a ratio of 61 parts A-side to100 parts B-side.

Example 32

B-side: 50.0 g  Transesterified polyol formed as in Example 27 3.0 gDipropylene glycol 1.5 g Water 0.6 g Dibutyltin diacetate (T1) -catalyst 0.3 g Tertiary block amine catalyst A-side: Modified monomericMDI (MONDUR ® MA-2903)

The B-side was combined with the A-side in a ratio of 74 parts A-side to100 parts B-side.

Example 33

B-side: 50.0 g  Transesterified polyol formed as in Example 27 3.0 gDipropylene glycol 1.5 g Water 0.2 g Silicon surfactant (AIR PRODUCTS ®DC193) 1.1 g Dibutyltin diacetate (T1) - catalyst A-side: Modifiedmonomeric MDI (MONDUR ® MA-2903)

The B-side was combined with the A-side in a ratio of 55 parts A-side to100 parts B-side.

Example 34

Transesterification: 50.0 g Blown soy oil  6.0 g 33% Glycerin and 66%Sorbitol reaction product mixture

Example 35

B-side: 50.0 g  Transesterified polyol formed as in Example 34 3.0 gDipropylene glycol 0.6 g Dibutyltin diacetate (T1) - catalyst A-side:Modified monomeric MDI (MONDUR ® MA-2903)

The B-side was combined with the A-side in a ratio of 61 parts A-side to100 parts B-side at a temperature of 148° F. for 3 minutes.

Example 36

Transesterification 20.0 g Glycerin 40.0 g Brown cane sugar

The above was heated at a temperature of 250° F. and mixed. 30 g of wetmass was recovered in a filter and removed.

Example 37

B-side: 50.0 g  Transesterified polyol formed as in Example 36 3.0 gDipropylene glycol 1.0 g Dibutyltin diacetate (T1) - catalyst A-side:Modified monomeric MDI (MONDUR ® MA-2903)

The B-side was combined with the A-side in a ratio of 67 parts A-side to100 parts B-side at a temperature of 171° F. for one minute.

Example 38

B-side: 50.0 g  Transesterified polyol formed as in Example 36 3.0 gDipropylene glycol 1.0 g Dibutyltin diacetate (T1) - catalyst A-side:Modified monomeric MDI (MONDUR ® MA-2903)

The B-side was combined with the A-side in a ratio of 67 parts A-side to100 parts B-side at a temperature of 146° F. for 1.5 minutes.

Example 39

B-side: 50.0 g  Transesterified polyol formed as in Example 36 3.0 gDipropylene glycol 0.5 g Dibutyltin diacetate (T1) - catalyst A-side:MONDUR ® MR light

The B-side was combined with the A-side in a ratio of 20 parts A-side to100 parts B-side at a temperature of 141° F. for 2 minutes.

Example 40

B-side: 50.0 g  Transesterified polyol formed as in Example 36 3.0 gDipropylene glycol 1.0 g Dibutyltin diacetate (T1) - catalyst A-side:MONDUR ® MR light

The B-side was combined with the A-side in a 1:1 ratio A-side to B-sideat a temperature of 152° F. and for 1 minute.

Example 41

Transesterification 350.0 g  Blown soy oil 60.0 g Glycerin 35.0 g Whitecane sugar

The above was heated at a temperature of 240° F.

Example 42

B-side: 50.0 g  Transesterified polyol formed as in Example 41(preheated to 101° F.) 3.0 g Dipropylene glycol 1.0 g Dibutyltindiacetate (T1) - catalyst A-side: Modified monomeric MDI (MONDUR ®MA-2903)

The B-side was combined with the A-side in a ratio of 61 parts A-side to100 parts B-side at a temperature of 193° F. for 30 seconds.

Example 43

B-side: 50.0 g  Transesterified polyol formed as in Example 42(preheated to 101° F.) 3.0 g Dipropylene glycol 0.8 g Dibutyltindiacetate (T1) - catalyst A-side: MONDUR ® MR light

The B-side was combined with the A-side in a ratio of 61 parts A-side to100 parts B-side and reached a temperature of 227° F. for 20 seconds.

Example 44

Transesterification 35.9 g Glycerin  6.9 g Cane sugar 20.0 gTrimethylolpropane (preheated to 190° F.)

30 g of the above mixture was combined with 300 g of blown soy oil.

Example 45

Step 1 Heated 60 g trimethylolpropane (melting point of about 58° C.,about 136.4° F.) to liquid Step 2 Heated 30 g water and added 30 g canesugar Step 3 Added 60 g water and cane sugar to 60 g trimethylolpropaneand slowly raised the heat over 3 hours to 290° F. This drove off thewater.

Example 46

B-side: 20.0 g Transesterified polyol formed as in Example 44  0.5 gDibutyltin diacetate (T1) - catalyst A-side: Modified monomeric MDI(MONDUR ® MA-2903)

The B-side was combined with the A-side in a ratio of 40 parts A-side to100 parts B-side.

Example 47

Transesterification 1000 g Glycerin  500 g Cane sugar

The above was mixed at a temperature of 230° F. for 20 minutes.

Example 48

Transesterification:  22.3 g Reaction product formed as in Example 47100.0 g Blown soy oil

The above mixture was heated at a temperature of 227° F. for 20 minutes.

Example 49

50 g Water 50 g Cane sugar

The above was mixed and heated at a temperature of 85° F. for 20minutes.

Example 50

Transesterification  20 g Reaction mixture formed as in Example 53 100 gBlown soy oil

The above was heated at a temperature of 185° F. for 20 minutes, andthen heated to a temperature of 250° F. for 80 minutes.

Example 51

B-side: 20.0 g Transesterified polyol formed as in Example 50  0.4 gDibutyltin diacetate (T1) - catalyst A-side: MONDUR ® MR light

The B-side was combined with the A-side in a ratio of 56 parts A-side to100 parts B-side.

Example 52

B-side: 20.0 g Transesterified polyol formed as in Example 50  0.8 gDibutyltin diacetate (T1) - catalyst A-side: MONDUR ® MR light

The B-side was combined with the A-side in a ratio of 54 parts A-side to100 parts B-side.

Example 53

Transesterification 3200 g Blown soy oil (5% sugar by volume)  48 g 67%Glycerin and 37% Cane sugar mixture

Example 54

B-side: 60.0 parts by weight  Transesterified polyol formed as inExample 19 40.0 parts by weight  Polyether Polyol (BAYER ® MULTRANOL ®3901) 5.0 parts by weight Dipropylene Glycol 2.0 parts by weightDibutyltin diacetate (T1) - catalyst 2.1 parts by weight Water 109.0parts by weight  Calcium Carbonate (filler) A-side: MONDUR ® MR light

The B-side was combined with the A-side in a ratio of 56 parts A-side to100 parts B-side.

Example 55

B-side: 50.0 g  Transesterified polyol formed as in Example 19 3.0 gDipropylene glycol 1.0 g Water 0.8 g Dibutyltin diacetate (T1) -catalyst 54.7 g  Calcium Carbonate (filler) A-side: Bayer Corporation'sMONDUR ® MA-2901 (Isocyanate)

The B-side was combined with the A-side in a ratio of 40 parts A-side to100 parts B-side.

Example 56

B-side: 40.0 g  Transesterified polyol formed as in Example 53 10.0 g Polyether polyol 1.5 g Dipropylene glycol 1.5 g Butanediol 1.0 g Water 55 g Calcium Carbonate (filler) A-side: Modified monomeric MDI(MONDUR ® MA-2903)

Example 57

Transesterification 70.0 g Trimethylolpropane 33.0 g Pentaethertrol 60.0g Sugar

The above was heated to a temperature of 237° F. and added 15.0 g ofthis reaction product to 100.0 g of blown soil oil.

Example 58

B-side: 50.0 g  Transesterified polyol formed as in Example 53 3.0 gDipropylene Glycol 1.0 g Dibutyltin Diacetate (T1) A-side: Modifiedmonomeric MDI (MONDUR ® MA-2903)

The B-side was combined with the A-side in a ratio of 41 parts A-side to100 parts B-side at a temperature of 151° F. for 1 minute.

Example 59

B-side: 50.0 g  Transesterified polyol formed as in Example 53 3.0 gDipropylene Glycol 1.0 g Dibutyltin Diacetate (T1) A-side: Modifiedmonomeric MDI (MONDUR ® MA-2903)

The B-side was combined with the A-side in a ratio of 61 parts A-side to100 parts B-side at a temperature of 177° F. for 1 minute.

Example 60

B-side: 50.0 g  Transesterified polyol formed as in Example 53 3.0 gDipropylene glycol 3.0 g Dibutyltin diacetate (T1) A-side: Modifiedmonomeric MDI (MONDUR ® MA-2903)

The B-side was combined with the A-side in a ratio of 45 parts A-side to100 parts B-side at a temperature of 165° F. for 10 seconds.

Example 61

Transesterification 200 g Blown soy oil  20 g Trimethylolpropane

The above was heated to a temperature of 220° F. for 30 minutes.

Example 62

B-side: 50.0 g  Transesterified polyol formed as in Example 61 3.0 gDipropylene Glycol 1.0 g Dibutyltin Diacetate (T1) A-side: Modifiedmonomeric MDI (MONDUR ® MA-2903)

The B-side was combined with the A-side in a ratio of 61 parts A-side to100 parts B-side at a temperature of 168° F. for 35 seconds.

Example 63

Transesterification: 200 g Blown soy oil  20 g Trimethylolpropane

The above was heated at a temperature of 325° F. for 1 hour. Thetrimethylolpropane did not dissolve completely.

Example 64

B-side: 50.0 g  Transesterified polyol formed as in Example 63 3.0 gDipropylene Glycol 1.0 g Dibutyltin Diacetate (T1) A-side: Modifiedmonomeric MDI (MONDUR ® MA-2903)

The B-side was combined with the A-side in a ratio of 61 parts A-side to100 parts B-side at a temperature of 151° F. for 1 minute.

Example 65

Transesterification 100.0 g Blown soy oil  5.9 g Trimethylolpropane

The above was heated at a temperature of 235° F.

Example 66

B-side: 50.0 g  Transesterified polyol formed as in Example 65 3.0 gDipropylene Glycol 1.0 g Dibutyltin Diacetate (T1) A-side: Modifiedmonomeric MDI (MONDUR ® MA-2903)

The B-side was combined with the A-side in a ratio of 61 parts A-side to100 parts B-side at a temperature of 162° F. for 1 minute.

Example 67

B-side: 50.0 g  Transesterified polyol formed as in Example 65 3.0 gDipropylene Glycol 1.0 g Dibutyltin Diacetate (T1) A-side: Modifiedmonomeric MDI (MONDUR ® MA-2903)

The B-side was combined with the A-side in a ratio of 61 parts A-side to100 parts B-side at a temperature of 166° F. for 1 minute.

Example 68

Transesterification 2000 g Blown soy oil  100 g Trimethylolpropane

The above was heated at a temperature of 200° F. for 2 hours.

Example 69

B-side: 50.0 g  Transesterified polyol formed as in Example 68 3.0 gDipropylene Glycol 1.0 g Dibutyltin Diacetate (T1) A-side: Modifiedmonomeric MDI (MONDUR ® MA-2903)

The above was heated at a temperature of 166° F. for 1 minute.

Example 70

B-side: 50.0 g  Transesterified polyol formed as in Example 68 4.0 gDipropylene Glycol 1.4 g Dibutyltin Diacetate (T1) 1.3 g Water A-side:Modified monomeric MDI (Mondur ® MA-2903)

Example 71

B-side: 50.0 g  Transesterified polyol formed as in Example 68 3.0 gDipropylene Glycol 1.0 g Dibutyltin Diacetate (T1) A-side: Modifiedmonomeric MDI (MONDUR ® MA-2903)

The B-side was combined with the A-side in a ratio of 61 parts A-side to100 parts B-side at a temperature of 172° F. for 1 minute.

Example 72

B-side: 50.0 g Transesterified polyol formed as in Example 68  2.0 gDibutyltin diacetate (T1) A-side: Modified monomeric MDI (MONDUR ®MA-2903)

The above was heated at a temperature of 135° F.

Example 73

Transesterification 200.0 g Blown soy oil  4.0 g Trimethylolpropane

The above was heated at a temperature of 205° F.

Example 74

B-side: 50.0 g Transesterified polyol formed as in Example 73  2.0 gDibutyltin diacetate (T1) A-side: Modified monomeric MDI (MONDUR ®MA-2903)

The B-side was combined with the A-side in a ratio of 45 parts A-side to100 parts B-side at a temperature of 126° F.

Example 75

Transesterification 400 g Blown soy oil  62 g 66.7% Glycerin and 33.3%cane sugar mixture

The above mixture was heated at an average temperature of 205° F.

Example 76

B-side: 40.0 g  Transesterified polyol formed as in Example 53 1.5 gDipropylene Glycol 1.5 g Butanediol 0.4 g Dibutyltin Diacetate (T1) 10.0g  Polyether Polyol (Bayer MULTRANOL ® 3901) ® 3901 A-side: Modifiedmonomeric MDI (MONDUR ® MA-2903)

The B-side was combined with the A-side in a ratio of 62 parts A-side to100 parts B-side.

Example 77

B-side: 40.0 g  Transesterified polyol formed as in Example 53 1.5 gDipropylene Glycol 1.5 g Butanediol 0.4 g Dibutyltin Diacetate (T1) 10.0g  Polyether Polyol (Bayer MULTRANOL ® 9151) A-side: Modified monomericMDI (MONDUR ® MA-2903)

The B-side was combined with the A-side in a ratio of 62 parts A-side to100 parts B-side.

Example 78

B-side: 40.0 g  Transesterified polyol formed as in Example 75 1.5 gDipropylene Glycol 1.5 g Butanediol 0.4 g Dibutyltin Diacetate (T1)A-side: Modified monomeric MDI (MONDUR ® MA-2903)

The B-side was combined with the A-side in a ratio of 42 parts A-side to100 parts B-side.

Example 79

B-side: 20.0 g Transesterified polyol formed as in Example 75  0.4 gDibutyltin Diacetate (T1) A-side: Modified monomeric MDI (MONDUR ®MA-2903)

The B-side was combined with the A-side in a ratio of 42 parts A-side to100 parts B-side.

Example 80

B-side: 100.0 g Transesterified polyol formed as in Example 75  2.9 gDibutyltin Diacetate (T1) A-side: Modified monomeric MDI (MONDUR ®MA-2903)

The B-side was combined with the A-side in a ratio of 44 parts A-side to100 parts B-side.

Example 81

Transesterification 350 g Blown soy oil  52 g 66.7% Glycerin and 33.3%cane sugar mixture

The above was heated at a temperature of 194° F. for 4 hours.

Example 82

B-side: 40.0 g Transesterified polyol formed as in Example 53  1.5 gDipropylene Glycol  1.5 g Butanediol  0.3 g Dibutyltin Diacetate (T1)10.0 g Polyether Polyol (BAYER ® MULTRANOL ® 3901) 97.0 g CalciumCarbonate (filler) A-side: Modified monomeric MDI (MONDUR ® MA-2903)

The B-side was combined with the A-side in a ratio of 62 parts A-side to100 parts B-side.

Example 83

B-side: 20.0 g  Transesterified polyol formed as in Example 53 1.5 gDipropylene Glycol 1.5 g Butanediol 0.4 g Dibutyltin Diacetate (T1) 0.4g Dibutyltin Dilaurate (T12) 8.0 g Polyether Polyol (BAYER ® MULTRANOL ®3901) A-side: MONDUR ® MR Light

The B-side was combined with the A-side in a ratio of 70 parts A-side to100 parts B-side.

Example 84

Transesterification 400.0 g  Blown soy oil  6.0 g Vinegar (to add acidicproton); hydrogen chloride may also be added 60.0 g 66.7% Glycerin and33.3% Cane sugar mixture

The above was heated at a temperature of ₂₁₀° F. for 1 hour.

Example 85

B-side: 40.0 g Transesterified polyol formed as in Example 84  0.8 gDibutyltin Diacetate (T1) A-side: Modified monomeric MDI (MONDUR ®MA-2903)

The B-side was combined with the A-side in a ratio of 42 parts A-side to100 parts B-side.

Example 86

B-side: 40.0 g Transesterified polyol formed as in Example 84  0.8 gDibutyltin Diacetate (T1) A-side: Modified monomeric MDI (MONDUR ®MA-2903)

The B-side was combined with the A-side in a ratio of 70 parts A-side to100 parts B-side.

Example 87

Transesterification First step: 80.0 g 66.7% Glycerin and 33.3% Canesugar  0.8 g Vinegar

The above was heated at a temperature of 260° F. for 30 minutes.

Second Step:

60 g of the above reaction product was reacted with 400 g blown soy oiland mixed for 30 minutes.

Example 88

B-side: 50.0 g Transesterified polyol formed as in Example 87  1.0 gDibutyltin diacetate (T1) A-side: Modified monomeric MDI (MONDUR ®MA-2903)

The B-side was combined with the A-side in a ratio of 42 parts A-side to100 parts B-side.

Example 89

B-side: 20.0 g Transesterified polyol formed as in Example 87  0.5 gDibutyltin diacetate (T1) 20.0 g BAYER ® MULTRANOL ® A-side: MONDUR ® MRLight

The B-side was combined with the A-side in a ratio of 92 parts A-side to100 parts B-side at a temperature of 240° F. for 20 seconds.

Example 90

B-side: 50.0 g Blown soy oil  1.7 g Dibutyltin diacetate (T1) A-side:Modified monomeric MDI (MONDUR ® MA-2903)

The B-side was combined with the A-side in a ratio of 42 parts A-side to100 parts B-side.

Example 91

Transesterification  50.0 g Blown soy oil 100.0 g BAYER ® MULTRANOL ®9185

The above was heated to a temperature of 100° F. for 5 hours.

Example 92

B-side: 50.0 g Transesterified polyol formed as in Example 91  0.7 gDibutyltin diacetate (T1) A-side: MONDUR ® MR Light

The B-side was combined with the A-side in a ratio of 56 parts A-side to100 parts B-side.

Example 93

Transesterification 80.0 g Blown soy oil 20.0 g Polyether Polyol BAYER ®MULTRANOL ® 3901

The above was heated to a temperature of 100° C.

Example 94

B-side: 50.0 g  Blown soy oil 0.8 g Dibutyltin Dilaurate (T12) 5.0 gButanediol A-side: Modified monomeric MDI (MONDUR ® MA-2903)

The B-side was combined with the A-side in a ratio of 64 parts A-side to100 parts B-side at a temperature of 167° F. for 90 seconds.

Example 95

B-side: 50.0 g Blown soy oil 15.0 g Butanediol  0.8 g DibutyltinDilaurate (T12) A-side: Modified monomeric MDI (MONDUR ® MA-2903)

The B-side was combined with the A-side in a ratio of 131 parts A-sideto 100 parts B-side at a temperature of 224° F. for 20 seconds.

Example 96

2000 g Transesterified polyol formed as in Example 80 6 g Dipropyleneglycol 6 g Butanediol 40 g Polyether Polyol (BAYER ® MULTRANOL ® 3901)

Example 97

B-side: 50.0 g Transesterified prepolymer polyol formed as in Example 96 0.3 g Dibutyltin Dilaurate (T12) A-side: Modified monomeric MDI(MONDUR ® MA-2903)

The B-side was combined with the A-side in a ratio of 62 parts A-side to100 parts B-side for 120 seconds.

Example 98

B-side: 50.0 g Transesterified prepolymer polyol formed as in Example 96 0.2 g Dibutyltin Dilaurate (T12) A-side: Modified monomeric MDI(MONDUR ® MA-2903)

The B-side was combined with the A-side in a ratio of 62 parts A-side to100 parts B-side for 160 seconds.

Example 99

B-side: 50.0 g Transesterified prepolymer polyol formed as in Example 96 0.4 g Dibutyltin Dilaurate (T12) A-side: Modified monomeric MDI(MONDUR ® MA-2903)

The B-side was combined with the A-side in a ratio of 62 parts A-side to100 parts B-side for 80 seconds.

Example 100

B-side: 40.0 g Transesterified prepolymer polyol formed as in Example 96 0.2 g Dibutyltin Dilaurate (T12) A-side: MONDUR ® MR Light mixed with15% blown soy oil for 120 seconds.

The B-side was combined with the A-side in a ratio of 62 parts A-side to100 parts B-side.

Example 101

Transesterification 400 g Blown soy oil  60 g 66.7% Glycerin and 33%Cane sugar mixture

The above was heated at a temperature of 198° F. for 5 hours.

Example 102

B-side: 50.0 g Transesterified polyol formed as in Example 101  0.8 gDibutyltin Dilaurate (T12) A-side: Modified monomeric MDI (MONDUR ®MA-2903)

The B-side was combined with the A-side in a ratio of 42 parts A-side to100 parts B-side at a temperature of 149° F. for 260 seconds.

Example 103

B-side: 40.0 g Transesterified polyol formed as in Example 81  0.9 gDibutyltin Dilaurate (T12) 10.0 g BAYER ® MULTRANOL ® A-side: MONDUR ®MR Light

The B-side was combined with the A-side in a ratio of 56 parts A-side to100 parts B-side at a temperature of 189° F. for 190 seconds.

Example 104

B-side: 40.0 g Transesterified polyol formed as in Example 81  3.0 gButanediol  0.9 g Dibutyltin Dilaurate (T12) 10.0 g BAYER ® MULTRANOL ®A-side: MONDUR ® MR Light

The above was heated at a temperature of 220° F. for 116 seconds.

Example 105

Transesterification 400 g Blown soy oil  60 g 66.7% Glycerin and 33.3%Cane Sugar

Example 106

B-side: 50.0 g Transesterified polyol formed as in Example 81  0.8 gDibutyltin Dilaurate (T12) A-side: Modified monomeric MDI (MONDUR ®MA-2903)

The B-side was combined with the A-side in a ratio of 70 parts A-side to100 parts B-side.

Example 107

B-side: 50.0 g Transesterified polyol formed as in Example 101  0.9 gDibutyltin Dilaurate (T12) A-side: Modified monomeric MDI (MONDUR ®MA-2903)

The B-side was combined with the A-side in a ratio of 14 parts A-side to100 parts B-side.

Example 108

Transesterification 200.0 g Blown soy oil  14.3 g Honey

The above was heated at a temperature of 200° F. for 3 hours.

Example 109

B-side: 50.0 g  Transesterified polyol formed as in Example 81 0.1 gDibutyltin Dilaurate (T12) 10.0 g  Polyether Polyol (BAYER ® MULTRANOL ®3901) 1.5 g Dipropylene glycol 1.5 g Butanediol A-side: Modifiedmonomeric MDI (MONDUR ® MA-2903)

The B-side was combined with the A-side in a ratio of 62 parts A-side to100 parts B-side.

Example 110

B-side: 40.0 g  Transesterified polyol formed as in Example 81 0.2 gDibutyltin Dilaurate (T12) 10.0 g  Polyether Polyol (BAYER ® MULTRANOL ®3901) 1.5 g Dipropylene glycol 1.5 g Butanediol 0.2 g Air Products DBU ®= urethane catalyst (1,8 Diazabicyclo[5.4.0]) A-side: Modified monomericMDI (MONDUR ® MA-2903)

The B-side was combined with the A-side in a ratio of 62 parts A-side to100 parts B-side.

Example 111

B-side: 80.0 g  Transesterified polyol formed as in Example 81 20.0 g Polyether Polyol (BAYER ® MULTRANOL ® 3901) 3.0 g Dipropylene glycol 3.0g Butanediol 0.4 g Air Products DBU ® = urethane catalyst (1,8Diazabicyclo[5.4.0]) A-side: Modified monomeric MDI (MONDUR ® MA-2903)

The B-side was combined with the A-side in a ratio of 62 parts A-side to100 parts B-side.

Example 112

B-side: 80.0 g  Transesterified polyol formed as in Example 81 20.0 g Polyether Polyol (Bayer ® Multranol ® 3901) 3.0 g Dipropylene glycol 3.0g Butanediol 0.6 g Air Products DBU ® = urethane catalyst (1,8Diazabicyclo[5.4.0]) A-side: Modified monomeric MDI (MONDUR ® MA-2903)

The B-side was combined with the A-side in a ratio of 62 parts A-side to100 parts B-side.

Example 113

B-side: 50.0 g Transesterified polyol formed as in Example 81  0.8 gDibutyltin Dilaurate (T12) 10.0 g Polyether Polyol (BAYER ® MULTRANOL ®3901) 62.0 g Calcium Carbonate filler A-side: MONDUR ® MR Light

The B-side was combined with the A-side in a ratio of 56 parts A-side to100 parts B-side.

Example 114

B-side: 50.0 g  Transesterified polyol formed as in Example 81 0.2 gDibutyltin Dilaurate (T12) 0.2 g Air Products DBU ® = urethane catalyst(1,8 Diazabicyclo[5.4.0]) A-side: 20% Modified monomeric MDI (MONDUR ®MA-2903) 80% MONDUR ® MR Light

The B-side was combined with the A-side in a ratio of 62 parts A-side to100 parts B-side.

Example 115

Transesterification 389.0 g Blown soy oil  13.0 g Dipropylene glycol 31.6 g Polyether Polyol (BAYER ® MULTRANOL ® 3901) 381.5 g DibutyltinDilaurate (T12)

Example 116

B-side: 40.0 g Transesterified polyol formed as in Example 81 10.0 gPolyether Polyol (BAYER ® MULTRANOL ® 9196)  0.4 g Dibutyltin Dilaurate(T12) A-side: 20.0 g Modified monomeric MDI (MONDUR ® MA-2903) 80.0 gMONDUR ® MR Light

The B-side was combined with the A-side in a ratio of 82 parts A-side to100 parts B-side.

Example 117

B-side: 40.0 g  Transesterified polyol formed as in Example 101 0.1 gDibutyltin Dilaurate (T12) 1.5 g Dipropylene glycol 10.0 g  PolyetherPolyol (BAYER ® MULTRANOL ® 3901) 0.4 g Air Products DBU ® = urethanecatalyst (1,8 Diazabicyclo[5.4.0]) A-side: Modified monomeric MDI(MONDUR ® MA-2903)

The B-side was combined with the A-side in a ratio of 72 parts A-side to100 parts B-side.

Example 118

B-side: 50.0 g Transesterified polyol formed as in Example 81  0.5 gDibutyltin Dilaurate (T12)  2.0 g Butanediol 20.0 g Polyether Polyol(BAYER ® MULTRANOL ® 9196) A-side: 20% Modified monomeric MDI (MONDUR ®MA-2903) 80% MONDUR ® MR Light

The B-side was combined with the A-side in a ratio of 88 parts A-side to100 parts B-side.

Example 119

B-side: 50.0 g Transesterified polyol formed as in Example 81 20.0 gPolyether Polyol (BAYER ® MULTRANOL ® 9196) 0.5 g Dibutyltin Dilaurate(T12) 2.0 g Dipropylene Glycol A-side: 20 g Modified monomeric MDI(MONDUR ® MA-2903) 80 g MONDUR ® MR Light

Example 120 Water Blown TDI Seating-Type Foam

B-side: 50.0 g  Transesterified blown soy oil 50.0 g  Conventionalpolyol (3 Functional, 28 OH, 6000 Molecular weight, 1100 viscosity) 0.8g Non-acid blocked Dibutyltin dilaurate catalyst 0.8 g Flexible blowingcatalyst (Bis(N,N,dimethylaminoethyl)ether), 1.0 g Flexible foam siliconsurfactant 1.0 g Water A-side: 2,4-Toluene Diisocyanate (TDI)

The B-side was combined with the A-side in a ratio of 40 parts A-side to100 parts B-side.

Example 121 Hydrocarbon Blown TDI Seating-Type Foam

B-side: 50.0 g  Transesterified blown soy oil 50.0 g  Conventionalpolyol (3 Functional, 28 OH, 6000 Molecular weight, 1100 viscosity) 0.8g Non-acid blocked Dibutyltin Dilaurate catalyst 0.8 g Flexible blowingcatalyst (Bis(N,N,dimethylaminoethyl)ether) 1.0 g Flexible foam siliconesurfactant 4.0 g Cyclopentane, or other suitable blowing agents A-side:2,4-Toluene Diisocyanate (TDI)

The B-side was combined with the A-side in a ratio of 40 parts A-side to100 parts B-side.

Example 122 Water Blown MDI Seating-Type Foam

B-side: 100.0 g  Transesterified blown soy oil 1.0 g Flexible foamsurfactant 1.6 g Non-acid blocked Dibutyltin Dilaurate catalyst 3.0 gWater A-side: 100% Isocyanate terminated PPG (polypropylene etherglycol) Prepolymer (19% NCO, 400 Viscosity, 221 Equivalent weight, 2Functional)

The B-side was combined with the A-side in a ratio of 65 parts A-side to100 parts B-side.

Example 123 Hydrocarbon Blown MDI Seating-Type Foam

B-side: 100.0 g  Transesterified blown soy oil 1.0 g Flexible foamsurfactant 1.6 g Non-acid blocked Dibutyltin Dilaurate catalyst 6.0 gCyclopentane, or other suitable blowing agent A-side: 100% Isocyanateterminated PPG (polypropylene ether glycol) Prepolymer (19% NCO, 400Viscosity, 221 Equivalent weight, 2 Functional)

The B-side was combined with the A-side in a ratio of 65 parts A-side to100 parts B-side.

Example 124 Water Blown Higher Rebound MDI Searing-Type Foam

B-side: 50.0 g  Transesterified blown soy oil 50.0 g  Conventionalpolyol (3-functional, 28 OH, 6000 molecular weight, 1100 viscosity) 1.0g Flexible foam surfactant 0.3 g Non-acid blocked Dibutyltin Dilauratecatalyst 0.4 g Non-acid blocked Alkyltin mercaptide catalyst 3.0 g WaterA-side: 100% Isocyanate terminated PPG (polypropylene ether glycol)Prepolymer (19% NCO, 400 Viscosity, 221 Equivalent weight, 2 Functional)

The B-side was combined with the A-side in a ratio of 62 parts A-side to100 parts B-side.

Example 125 Hydrocarbon Blown Higher Rebound MDI Searing-Type Foam

B-side: 50.0 g  Transesterified blown soy oil 50.0 g  Conventionalpolyol (3 Functional, 28 OH, 6000 Molecular weight, 1100 Viscosity) 1.0g Flexible foam surfactant 0.3 g Non-acid blocked Dibutyltin Dilauratecatalyst 0.4 g Non-acid blocked Alkyltin mercaptide catalyst 6.0 gCyclopentane, or other suitable blowing agents A-side: 100% Isocyanateterminated PPG (polypropylene ether glycol) Prepolymer (19% NCO, 400Viscosity, 221 Equivalent weight, 2 Functional)

The B-side was combined with the A-side in a ratio of 62 parts A-side to100 parts B-side.

Example 126 Water Blown Lightweight Rigid Urethane Material

B-side: 50.0 g  Transesterified blown soy oil 1.2 g Non-acid blockedDibutyltin Dilaurate catalyst 1.0 g Water A-side: 100% Polymeric MDI(Methylenebisdipenyl diisocyanate) (31.9% NCO, 200 Viscosity, 132Equivalent weight, 2.8 Functional)

The B-side was combined with the A-side in a ratio of 70 parts A-side to100 parts B-side.

Example 127 Hydrocarbon Blown Lightweight Rigid Urethane Material

B-side: 100.0 g  Transesterified blown soy oil 1.2 g Non-acid blockedDibutyltin Dilaurate catalyst 3.0 g Cyclopentane, or other suitableblowing agents A-side: 100% Polymeric MDI (Methylenebisdipenyldiisocyanate) (31.9% NCO, 200 Viscosity, 132 Equivalent weight, 2.8Functional)

The B-side was combined with the A-side in a ratio of 70 parts A-side to100 parts B-side.

Example 128 Dense Rigid Urethane Material

B-side: 100.0 g Transesterified blown soy oil  1.2 g Non-acid blockedDibutyltin Dilaurate catalyst A-side: 100% Polymeric MDI(Methylenebisdipenyl diisocyanate) (31.9% NCO, 200 Viscosity, 132Equivalent weight, 2.8 Functional)

The B-side was combined with the A-side in a ratio of 70 parts A-side to100 parts B-side.

Example 129 Very Dense Rigid Urethane Material

B-side: 100.0 g Transesterified blown soy oil  1.2 g Non-acid blockedDibutyltin Dilaurate catalyst A-side: 100% Polymeric MDI(Methylenebisdipenyl diisocyanate) (31.9% NCO, 200 Viscosity, 132Equivalent weight, 2.8 Functional)

The B-side was combined with the A-side in a ratio of 110 parts A-sideto 100 parts B-side.

Example 130 Semi-Flexible Carpet Backing Material

B-side: 80.0 g  Transesterified blown soy oil 20.0 g  Conventionalpolyol (2 Functional, 28 OH, 4000 Molecular weight, 820 Viscosity) 0.2 gNon-acid blocked Dibutyltin Dilaurate catalyst 0.5 g Non-acid blockedAlkyltin mercaptide catalyst 4.0 g Dipropylene glycol A-side: 100%Monomeric MDI (methylenebisdiphenyl diisocyanate) (23% NCO, 500Viscosity, 183 Equivalent weight, 2 Functional)

The B-side was combined with the A-side in a ratio of 45 parts A-side to100 parts B-side.

Example 131 Semi-Flexible Carpet Backing Material

B-side: 80.0 g  Blown soy oil 20.0 g  Conventional polyol (2 Functional,28 OH, 4000 Molecular weight, 820 Viscosity) 0.2 g Non-acid blockedDibutyltin Dilaurate catalyst 0.5 g Non-acid blocked Alkyltin mercaptidecatalyst 4.0 g Dipropylene glycol A-side: 50% 4,4-MDI(methylenebisdiphenyl diisocyanate) Isocyanate 50% 2,4-MDI(methylenebisdiphenyl diisocyanate)Isocyanate mixture (33.6% NCO, 10Viscosity, 125 Equivalent weight, 2 Functional)

The B-side was combined with the A-side in a ratio of 34 parts A-side to100 parts B-side.

Example 132 Flexible Carpet Padding Material

B-side: 85.0 g  Transesterified blown soy oil 7.5 g Conventional polyol(3 Functional, 28 OH, 4000 Molecular weight, 1100 Viscosity) 7.5 gConventional polyol (4 Functional, 395 OH, 568 Molecular weight, 8800Viscosity) 0.1 g Non-acid blocked Dibutyltin Dilaurate catalyst 0.2 gNon-acid blocked Alkyltin mercaptide catalyst 2.0 g Dipropylene glycolA-side: 100% Isocyanate terminated PPG (polypropylene ether glycol)Prepolymer (19% NCO, 400 Viscosity, 221 Equivalent weight, 2 Functional)

The B-side was combined with the A-side in a ratio of 70 parts A-side to100 parts B-side.

Example 133 Fast-Set Hard Skin Coating Material

B-side: 100.0 g  Transesterified blown soy oil 1.0 g Flexible foamsurfactant 0.8 g Non-acid blocked Dibutyltin Dilaurate catalyst 0.8 gFast acting Amicure DBU ® (Bicyclic Amidine) catalyst A-side: 100%Isocyanate terminated PPG (polypropylene ether glycol) Prepolymer (19%NCO, 400 Viscosity, 221 Equivalent weight, 2 Functional)

The B-side was combined with the A-side in a ratio of 68 parts A-side to100 parts B-side.

Example 134 Wood Molding Substitute Material

B-side: 100.0 g  Transesterified blown soy oil 2.0 g Trimethylolpropane1.0 g Non-acid blocked Dibutyltin Dilaurate catalyst A-side: 100%Polymeric MDI (methylenebisdiphenyl diisocyanate) (31.9% NCO, 200Viscosity, 132 Equivalent weight, 2.8 Functional)

The B-side was combined with the A-side in a ratio of 80 parts A-side to100 parts B-side.

Example 135 Semi-Rigid Floral Foam Type Material

B-side: 100.0 g  Transesterified blown soy oil 0.5 g Non-acid blockedDibutyltin Dilaurate catalyst 0.5 g Fast acting Amicure DBU (Bicyclicamidine) catalyst 5.0 g Water A-side: 100% Polymeric MDI(methylenebisdiphenyl diisocyanate) (31.9% NCO, 200 Viscosity, 132Equivalent weight, 2.8 Functional)

The B-side was combined with the A-side in a ratio of 70 parts A-side to100 parts B-side. A colorant (green) may be added if desired.

While vegetable oil based transesterified polyols are preferred inurethane production, an alternative embodiment of the present inventionincludes a cellular material that is the reaction product of an A-sideand a B-side, where the A-side is comprised of a diisocyanate and theB-side comprises a vegetable oil, or a blown vegetable oil, across-linking agent comprised of a multi-functional alcohol, and acatalyst. This alternative further comprises a method for preparing acellular material comprising the reactive product of an A-side comprisedof a prepolymer diisocyanate and a B-side. The B-side comprises a firstvegetable oil, a cross-linking agent comprised of a multifunctionalalcohol, a catalyst, and a blowing agent.

There are several methods of application and production available foreither the vegetable oil based transesterified polyurethane or thealternative non-transesterified vegetable oil-based polyurethane. Asshown in FIG. 1 (the simplified processes shown in FIGS. 1-4 proceedfrom left to right), the tuft/primary backing assembly, commonlyreferred to as griege goods, is metered to bow and weft straighteningstation where the bow and weft are straightened to the alignment fibers.Griege goods are then conveyed to bed plate pre-coat applicators wherepre-coat polyurethane carpet backing application are then applied andthen sized through doctor blades. As in other polyurethane applications,the pre-coat polyurethane carpet backing application acts as an adhesivethereby holding the tuft of carpet so the tufts remain engaged with thepolypropylene primary backing.

The pre-coat polyurethane carpet backing application comprises thereaction product of a pre-coat A-side comprising an isocyanate and apre-coat B-side. As discussed previously, the A-side pre-coat may alsocomprise a pre-coat prepolymer of crude vegetable oil, blown vegetableoil, or transesterified vegetable oil. The pre-coat B-side may compriseany of the aforementioned bio-based urethane systems. In one embodimentof the present invention, the pre-coat B-side comprises a petroleumbased polyol. In another embodiment, the pre-coat B-side comprises apre-coat vegetable oil, a pre-coat cross-linking agent, and a pre-coatcatalyst. In yet another embodiment, the pre-coat B-side comprises thereaction product of a pre-coat esterified polyol and a backing materialvegetable oil where the pre-coat esterified polyol comprises thereaction product of a first pre-coat multifunctional compound and asecond pre-coat multifunctional compound.

The carpet material is then transported to an electric or a gas preheatoven, which serves to cure the pre-coat. Next, the carpet material isconveyed to a backing material applicator.

At this point, a backing material is applied. The backing material istypically a foam cushioning material. The backing material comprises thereaction product of a backing material A-side comprising a backingmaterial isocyanate and a backing material B-side. As with the pre-coatB-side, any of the aforementioned bio-based urethane systems may beemployed or petroleum based systems. In one embodiment of the presentinvention, the backing material B-side comprises a petroleum basedpolyol. In yet another embodiment, the backing material B-side comprisesa backing material vegetable oil, a backing material cross-linker (chainextender), and a backing material catalyst. In another embodiment of thepresent invention, backing material B-side comprises the reactionproduct of a backing material vegetable oil and a backing materialesterified polyol where the backing material esterified polyol comprisesthe reaction product of a first backing material multifunctionalcompound and a second backing material multifunctional compound.

The carpet material is next sized through a final doctor blade. Thefinal doctor blade is used to set off, or even out, the carpet material,where the carpet material is then transported toward and through asecond electric or gas curing oven to finally cure the pre-coat and thebacking material.

An additional method of application is to position the carpet materialso the tufts are facing upward, as shown in FIG. 2. The process shown inFIG. 2 is very similar to the process shown in FIG. 1 as describedabove, but with some distinctions. First, while the pre-coat may beapplied from above, as shown in the production line depicted in FIG. 1,the pre-coat may also be applied from below the production line. Ineither case, the pre-coat is applied to the bottom surface of the griegegoods. Second, once the pre-coat has been cured, an adhesive may beapplied to the pre-coat and previously formed backing material, adheredto the bottom surface of the griege goods preferably by pressure rollingthe previously formed backing material into contact with the adhesive.

FIG. 3 shows another variation of the carpet processing line where thepre-coat is applied to the bottom surface of the griege goods and thepreviously formed backing material is adhered to the bottom surface ofthe griege goods preferably by pressure rolling the previously formedbacking material into contact with the adhesive.

FIG. 4 shows yet another variation of the carpet processing line, whichis similar to the process described with respect to FIG. 1, but wherethe pre-coat and backing material are applied from above the productionline.

With the particularly advantageous features of the bio-basedpolyurethane of the present invention, it has been found that specificcharacteristics, such as padding, resilience, padding density, and otherdimensional characteristics may be obtained in a very highly selectiveand particularly advantageous manner, as opposed to polyurethanes of theprior art. For example, several carpets of the prior art utilize calciumcarbonate or other similar material as a filler to add weight to thecarpet, whereas the bio-based polyurethane carpets of the presentinvention do not. When calcium carbonate is added, the calcium carbonateis added to the B-side mixture from about 15 minutes to about 2 daysbefore the B-side utilizing the calcium carbonate is used. The calciumcarbonate is preferably agitated to keep it properly in suspension.Additionally, there are advantages in the application methods utilizedin making and applying the bio-based polyurethane. Another significantadvantage of manufacturing the bio-based carpet material as opposed topetroleum based polyurethanes relates to curing oven temperatures. Theovens typically used in the prior art (petroleum based carpet process)process reach a temperature of about 300° F., which consumesapproximately 3.5 million BTUs per hour. When the present invention isemployed, the curing ovens typically only need to reach a temperature offrom about 180° F., which, by contrast, only consumes approximately1-1.5 million BTUs per hour.

The above description is considered that of the preferred embodimentsonly. Modifications of the invention will occur to those skilled in theart and to those who make or use the invention. Therefore, it isunderstood that the embodiments shown in the drawings and describedabove are merely for illustrative purposes and not intended to limit thescope of the invention, which is defined by the following claims asinterpreted according to the principles of patent law, including thedoctrine of equivalents.

1. A method of making a carpet material comprising: providing tufts, a backing, a pre-coat, and a backing material wherein the pre-coat comprises the reaction product of a pre-coat A-side comprising a pre-coat isocyanate and a pre-coat B-side comprising a polyol derived from petroleum, a pre-coat cross-linking agent, and a pre-coat catalyst and wherein the backing material comprises the reaction product of a backing material A-side comprising an isocyanate and a backing material B-side comprising a vegetable oil, a cross-linker, and a catalyst; engaging the tufts and the primary backing thereby forming griege goods having a top and bottom surface; applying the pre-coat onto the bottom surface of the griege goods; curing the pre-coat; and applying the backing material to the bottom surface of the griege goods.
 2. The method of claim 1 further comprising curing the backing material.
 3. The method of claim 1, wherein the pre-coated carpet material is cured using a curing oven.
 4. The method of claim 3, wherein the curing oven temperature is about 180° F. to about 220° F.
 5. The method of claim 3, wherein the curing oven generates heat electrically or generates heat using a fossil fuel.
 6. The method of claim 1, wherein the vegetable oil comprises a blown soybean oil.
 7. The method of claim 1 further comprising subjecting the griege goods to a bow and weft straightening station thereby straightening the tufts.
 8. The method of claim 1, wherein the application of the pre-coat is applied by spraying the pre-coat A-side and the pre-coat B-side onto the bottom surface of the griege goods.
 9. The method of claim 1, wherein the backing material is applied by spraying the backing material A-side and the backing material B-side on the bottom surface of the griege goods.
 10. The method of claim 1, wherein the vegetable oil comprises a blown soybean oil.
 11. The method of claim 1, wherein the vegetable oil comprises at least one vegetable oil chosen from the group consisting of palm oil, safflower oil, sunflower oil, canola oil, rapeseed oil, cottonseed oil, linseed oil, and coconut oil.
 12. The method of claim 1, wherein the cross-linker comprises at least one cross-linker chosen from the group consisting of ethylene glycol, 1,4 butanediol, diethanol amines, ethanol amines, tripropylene glycol, aliphatic amine tetrol, or mixtures thereof. 